Oxazoline or oxazine acetoacetate aqueous coating compositions

ABSTRACT

A novel compound having the formula:  
                 
 
     wherein R is an alkyl group containing 1-5 carbon atoms or an aryl, substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl, alkylether-aryl or O; R 1  and R 2  are hydrogen or a methyl group; X is O, NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, or O—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl, NR″ is O-alkyl-ONH,  
                 
 
     wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.  
     The compound of this invention is useful as a monomer which can be polymerized and/or copolymerized by catonic polymerization.  
     Polymers and copolymers produced in this invention can be crosslinked and are useful in coatings, inks, overprint varnishes, and surface treatment applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] NONE

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0002] NONE

BACKGROUND OF THE INVENTION

[0003] 1. Technical Field

[0004] This invention relates to an aqueous coating composition such ascoatings, inks, coverprint varnish and surface treatment applicationscontaining an oxazoline or oxazine acetoacetate polymer.

[0005] 2. Background Art

[0006] In the following description of the prior art and in theExamples, the parenthetical numbers are described in the followingReference section. Acetoacetamide, acetoacetanilide, and acetoacetatefunctionalized chemicals are readily available, via reaction of aminesor hydroxyl substituted molecules with diketene (1-3), alkylacetoacetates, or the readily used acetoacetalation compound2,2,6-trimethyl-1,3-dioxin-4-one, which is prepared from reaction ofdiketene with acetone (2,4). Organic compounds or polymers with theacetoacetamide, acetoacetanilide, or acetoacetate type functionality areknown to react with a variety of other functional chemicals (1-5),including such things as amines, aldehydes, and isocyanates, givingvarious adducts in excellent yields at low reaction temperatures (2).Also, the acetoacetamide, acetoacetanilide, or acetoacetate group, withamine catalysts, will combine readily with the acrylate functionality,via what is commonly called the Michael addition reaction (2,5,6).Further, these acetoacetanilide, acetoacetamide, or acetoacetate groupsare known to readily react with various metal compounds, such as CaO,Ca(OH)₂, BaO, CoCl₂, NiCI₂, etc. to form metal complexes (1,3), wherethe chemistry has been used to prepare polymeric catalysts (2,7,8) andcrosslinked coatings (6,9-1 1). These chemicals with the acetoacetamide,acetoacetanilide, and/or acetoacetate functionality, which have threeactive centers, have found extensive utility in the formation ofmetal-complexes, manufacture of dyes and synthesis of heterocycles(1-3).

[0007] It is well known that cyclic imino ethers, such as oxazolines andoxazines will undergo cationic, ring-opening polymerizations (12) andzwitterionic copolymerization with such things as acrylic acid,maleimides, anhydrides, lactones, etc. (13-17). It is also well knownthat molecules with the oxazoline or oxazine residues will undergoring-opening reactions with compounds such as carboxylic acids, thiols(HS-groups), phenols, alkyl halides, etc., giving 1-to-1 adducts(18-24), allowing for step-growth copolymerizations to be readilyachieved with difunctional monomers. Further, it has been shown thatalkyl halides will initiate ring-opening polymerization of cyclic iminoethers, as well as give 1:1 adducts (18, 25). Thus oxazolines andoxazines are excellent intermediates for synthesis of variety ofpolymeric materials, both thermoplastics and thermosets, by chain-growthand step-growth polymerization mechanisms or combinations thereof. Inaddition, the synthesis and polymerization of oxazoline and oxazinemethacrylate aqueous coating compositions are also known (27).

REFERENCES

[0008] 1. U.S. Pat. No. 3,304,328 (Feb. 14, 1967) to FMC Corporation.

[0009] 2. N. Moszner, U. Salz, V. Rheinberger, MACROAKRON '94, 35thIUPAC Int. Symp. on Macromolecules, Jul. 11-15, 1994 paper.

[0010] 3. S. M. Hussain, A. M. El-Reedy, S. A. El-Sherabasy, J.Heterocyclic Chem., 25, 9-22 (1988).

[0011] 4. Wacker Chemicals (USA), Inc. literature, p. 16.

[0012] 5. R. J. Clemens, J. S. Witzman, F. Del Rector, Communications ofEastman Chemical Products, Inc.

[0013] 6. K. J. Edgar, K. M. Arnold, W. W. Blount, J. E. Lawniczak, andD. W. Lowman, Macromolecules 1995, 28, 4122-4128.

[0014] 7. T. Sato, A. Morita, I. Kamiya, T. Ota, Makromol. Chem., RapidComm. 11 (1990) 553.

[0015] 8. R. Ran, D. Fu, J. Macromol. Sci.-Chem. A27 (1990) 625.

[0016] 9. D. L. Trumbo, Polymer Bull. 26 (1991) 265,481.

[0017] 10. J. R. Grawe, B. G. Bufkin, J. Coatings Technol. 52 (1980) 73.

[0018] 11. U.S. Pat. No. 4,247,671 (Jan. 27, 1981) to Rohm and Haas Co.

[0019] 12. S. Kobayashi and T. Saegusa, Encyclopedia of Polymer Scienceand Engineering, Wiley & Sons, New York, Vol. 4, pp. 525-537, 1986.

[0020] 13. G. Odian, M. P. O'Callaghan, C. K. Chien, P. Gunatillake, M.Periyasay and D. L. Schmidt, Macromolecules, 23(4), 918-927 (1990).

[0021] 14. C. I. Simionescu, et.al., Polymer. Bull. (Berlin), 14(1),79-83 (1985).

[0022] 15. T. Saegusa, Makromol. Chem., Suppl., 4, 73-84 (1981).

[0023] 16. B. L. Rivas and G. D. Pizarro, Eur. Polym. J., 25(10),1001-1005 (1989).

[0024] 17. G. S. Canessa, A. S. Pooley, M. Parra and B. L. Rivas, Polym.Bull. (Berlin),

[0025] 11(5), 465-70 (1984).

[0026] 18. J. A. Frump, Chem. Rev., 71(5), 483-505 (1971).

[0027] 19. U.S. Pat. No. 3,758,62, (Sep. 11, 1973), to Dow Chemical.

[0028] 20. U.S. Pat. No. 4,600,766 (Jul. 15, 1986) to Takeda ChemicalCo.

[0029] 21. T. Nishikubo, T. Iizawa and A. Tokairin, Mackromol. Chem.,185, 1307-1316 (1984).

[0030] 22. T. Kagiya, S. Narisawa, T. Maeda and K. Fukui, PolymerLetters, 4, 257-260 (1966).

[0031] 23. U.S. Pat. No. 4,430,491 (Feb. 7, 1984) to Ashland ChemicalCo.

[0032] 24. B. M. Culbertson, M. L. Deviney, O. Tiba and D. D. Carlos,33rd SAMPE Symp., Mar. 7-10, pp. 1530-1545 (1988), Ibid. ₃₄th SAMPESymp. May 8-11, 1989. PP.2483-2497.

[0033] 25. S. Kobayashi, H. Uyama, Y. Narita and J. Ishiyama,Macromolecules, 25(12), 3232-3236 (1992).

[0034] 26.H. Witte and W. Seelinger, Liebigs Arn. Chem., 996-1009(1974).

[0035] 27.H. A. A. Rasoul, D. B. Obuchowski, D. L. Trumbo, B. M.Culbertson, and Y. Xue, Oxazoline Hydrolysis, Synthesis andPolymerization of a New Oxazoline Methacrylate, PP. 871-872 (1997).

[0036] The prior art fails to disclose chemical compositions, monomericor polymeric having both the cyclic imino ether and the acetoacetamide,acetoacetenilide or acetoacetate residues on the same molecule.

SUMMARY OF THE INVENTION

[0037] The novel compound of this invention has the following formula:

[0038] wherein R is an alkyl group containing 1-5 carbon atoms or anaryl, substituted aryl, substituted or unsubstituted heteroaryl,alkyl-aryl, alkylether-aryl or O; R. and R₂ are hydrogen or a methylgroup; X is O, NH, NR′ wherein R′ is an alkyl group containing 1-5carbon atoms, or O—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl, NR″is O-alkyl-ONH, or

[0039] wherein each instance alkyl contains 1-5 carbon atoms and n is 0or 1.

[0040] The compounds of this invention are monomers which may bepolymerized or copolymerized, via cationic, ring-opening polymerizationof the cyclic imino ether residues, producing polymers with pendantacetoacetamide, acetoacetanilide and/or acetoacetate groups. Polymers ofthe aforesaid type may be readily crosslinked, via a variety ofreactions as explained in the background art, to produce crosslinkedmaterials useful in coatings, adhesives, and other applications.Further, these monomers and polymers are shown to readily form metalcomplexes with a variety of metal salts, giving in many cases, highlycolored monomer-metal or macromolecular-metal complexes.

[0041] Referring to the previous formula, in the instance where R isaryl, X is NH, R₁ and R₂ are H and n is 0, this compound can be readilyprepared by reacting an aminophenyl oxazoline with diketene. In theinstance where R is aryl, X is NH, R. and R₂ are H and n is1,2-(4-aminophenyl) oxazine was reacted with diketene. The compoundwhere R is aryl, X is NR′, R₁ and R₂ are H and n is 0, this compound isprepared by reacting aminobenzonitrile with an alkyl iodide to obtain analkylaminobenzonitrile which is treated with ethanolamine to obtainalkylaminophenyl oxazoline. The resulting oxazoline compound issubsequently treated with 2, 2, 6-trimethyl-1,3-dioxin-4-one (TDO). Thecompound where R is aryl, X is NH, R, R₁ and R₂ are CH₃ and n is 0 isprepared by reacting ethylaminobenzoate with methylaminopropanol toyield a dimethyl derivative of aminophenyl oxazoline with the resultingoxazaline treated with TDO. The compound where R is alkyl, X is alkyl,R₁ and R₂ are hydrogen and n is 0 is prepared by reacting an alkylaminoalkylnitrile with ethanolamine to obtain alkylamino alkyloxazoline whichis subsequently treated with TDO. As to the compound where R, R₁, R₂ andn are as immediately and previously described but X is O-alkyl, it isobtained by reacting hydroxyalkyl oxazoline and TDO. In those instanceswhere R is aryl, R₁ and R₂ are hydrogen, n is 0 and X is O-alkyl-O,O-alkyl-CNH or

[0042] the following procedures were employed. Where X is O-alkyl-O,hydroxy-alkylphenyl oxazoline was reacted with TDO; where X isO-alkyl-CONH aminophenyl oxazoline was reacted with an alkyllactoneresulting in a hydroxyalkyl substituted amide of the oxazoline compoundwhich is subsequently treated with TDO; where X is

[0043] aminophenyl oxazoline was treated with an alkylene carbonate toobtain an intermediate carbamate deriviative which is subsequentlytreated with diketene.

[0044] To synthesize substituted aryl oxazolines, a substitutedaminobenzonitrile such as methyl substituted aminobenzonitrile isreacted with 2-aminoethanol in the presence of a zinc acetate catalystas set forth in Example 1 to provide an amino and methyl substitutedphenyloxazoline. The resulting substituted phenylaxazoline is reactedwith diketene in the manner of Example 4 to produce the desiredsubstituted aryl oxazoline. As indicated, the substituents on the phenylgroup can be alkyl and other functionalties can include nitro andhydroxyl.

[0045] To prepare the compounds of general formula where R isheteroaryl, a heterogroup of the formula:

[0046] is reacted with 2-aminoethanol as previously described to resultin a compound of the formula:

[0047] which is subsequently reacted with diketene. In the foregoingformula X=sulfur, oxygen, or NH or NR where R is alkyl and Y=hydrogen,bromine, chlorine, iodine fluorine, amino or hydroxyl.

[0048] To prepare compounds of the general formula where R isalkyl-aryl, a compound of the formula:

[0049] is reacted with 2-aminoethanol as previously described to resultin:

[0050] which is subsequently heated with diketene to produce the desiredalky-aryl substituted or unsubstituted acetoacetoxazoaline. In thisinstance X=hydrogen, carboxyl, halogen, alkyl or aryl.

[0051] To synthesize compounds of the general formula where R isalkylether-aryl, a hydroxybenzonitrile is reacted with 2-aminoethanol aspreviously described to result in a hydroxy substituted phenyloxazoline.This intermediate oxazoline is reacted with, for example ethylene oxide,to produce a compound of the formula:

[0052] which is further reacted with diketene to produce the desiredalkylether-aryl substituted acetoacetate oxazoline.

[0053] The term “alkyl” as used herein means an alkyl group having 1-5carbon atoms.

[0054] The Examples which follow are intended as an illustration ofcertain preferred embodiments of the invention, and no limitation of theinvention is implied.

EXAMPLE 1 2-(4-Aminophenyl)oxazoline (4-APOXO)

[0055] Using known procedures for the synthesis of cyclic imino ethersfrom nitriles (18,26), 4-aminobenzonitrile was treated with an excess of2-aminoethanol (1 part nitrile/2 parts aminoalcohol) in refluxingxylene, with 3.5 wt. % zinc acetate catalyst, with all under a slownitrogen stream. The solution was heated until no NH₃ was detected inthe off gas. After removal of the xylene, the crude solid product wasobtained in high yield. The crude product was recrystallized fromacetonitrile to obtain an 82% yield of white, crystalline 4-APOXO havingmp 163-165° C., reported 158-160° C. The structure of the monomer wasconfirmed by FT-IR and ¹H NMR. Structure of 4-APOXO is as follows:

EXAMPLE 2 2-(3-aminophenyl) oxazoline (3-APOXO)

[0056] Example 1 procedure was followed starting with3-aminobenzonitrile in place of the 4-amino compound, providing white,crystalline APOXO isomer in a 75% yield, with mp 126-128° C. FT-IR and¹H NMR confirmed the structure shown below:

EXAMPLE 3 2-(4-aminophenyl) oxazine (4-APOXI)

[0057] While this monomer is new to the literature, it is obvious themonomer may be made by published techniques used for Example 1 and 2compositions. Example 1 procedure was followed, with replacement of the2-aminoethanol by 3-aminopropanol (3-hydroxypropyl amine) for theoxazine synthesis procedure. The heretofore unreported crystalline4-APOXI, with mp 177-178° C., was obtained in 92% yield. The structure,shown below, was confirmed by elemental analysis, FT-IR and ¹H NMR.

EXAMPLE 4 2-(4-acetoacetanilide)oxazoline (4-AAOXO)

[0058] To a stirred solution of 4-APOXO, 20.4 g (0.136 mol), in 280 mlof tetrahydrofuran (THF), contained in a 500 ml round bottom flaskfitted with a reflux condenser and N₂ sparge tube, was added 10.8 ml(0.14 mol) of diketene in dropwise fashion, keeping the temperature at0-5° C. After 30 min, the temperature was allowed to rise to roomtemperature and the flask and contents allowed to sit for several hours.Evaporation of the solvent produced the crude, solid product inessentially quantitative yield. Recrystallization from acetonitrileproduced white, crystalline 4-AAOXO with mp 171-172° C. Elementalanalysis, FT-IR and ¹H NMR confirmed the structure of the heretoforeunreported monomer, as shown below:

EXAMPLE 5 2-(4-acetoacetanilide) oxazoline (4-AAOXO)

[0059] This Example illustrates an alternative synthesis of the abovecompound. 4-APOXO was reacted with t-butyl acetoacetate to yield 4-AAOXOin excess of 85% acording to the following reaction conditions: 30 g of4-APOXO were charged to a 500 ml round bottom flask equipped with amechanical stirrer, thermometer, Dean-Stark trap and reflux condenser.200 ml of xylene was added followed by 29.3 g of t-butyl acetoacetate.The reaction mixture was heated with stirring to 105° C. The rapidevolution of t-butanol began at this point and continued for 15-20minutes. The solvent was removed under reduced pressure and the solidresidue of the desired product was recrystallized twice fromacetonitrile and had a m.p. 170-171° C.

EXAMPLE 6 2-(4-acetoacetanilide) oxazoline (4-AAOXO)

[0060] This is a duplication of Example 4, except using differentstarting material. A 250 ml three-neck, round bottom flask was fittedwith a nitrogen gas inlet tube, magnetic stirrer, thermometer, andcondenser. 4-APOXO, 8.0 g (54 mmol), was mixed with2,2,6-trimethyl-1,3-dioxin-4-one (TDO), 8.0 ml (61 mmol), and 120 ml ofxylene. The solution was heated at reflux, under a slow nitrogen stream,for 4 hrs. On cooling, the crude 4-AAOXO precipated from solution. The4-AAOXO was collected, washed with diethyl ether, and dried in a vacuumto obtain the slightly yellow, crystalline monomer in 83% yield, havingmp 169-171° C. FT-IR and ¹H NMR confirmed the product to be the same asthat prepared in Example 4.

EXAMPLE 7 2-(3-acetoacetanilide)oxazoline (3-AAOXO)

[0061] Using Example 4 procedure, 3-APOXO was treated with a slightexcess of diketene to produce 3-AAOXO in 65% yield, with therecrystallized waxy solid having mp 77-78° C. Elemental, FT-IR and ¹HNMR confirmed the 3-AAOXO structure, as shown below:

EXAMPLE 8 2-(4-acetoacetanilide)oxazine (4-AAOXI)

[0062] Using Example 4 procedure, 4-APOXI was treated with a slightexcess of diketene to produce crude 4-AAOXI in essentially quantitativeyield. Recrystallization from acetonitrile gave the new monomer in 88%yield, having mp 133-134° C. The structure, shown below, was confirmedby elemental analysis, FT-IR and ¹H NMR spectroscopy.

EXAMPLE 9 N-Methyl-N-[4-(2-oxazolin-2-yl) phenyl]acetoacetamide

[0063] This compound was prepared by treating 4-aminobenzonitrile with aslight excess, on a molar equivalents basis, of methyl iodide intetrahydrofuran solvent for 4 hrs at room temperature. Removal of theTHF and other volatiles, followed by recrystallization, gave a 76% yieldof 4-(N-methyl)aminobenzonitrile, mp 85-87° C. Using Example 1procedure, the aforesaid substituted nitrile was treated withethanolamine to obtain a 70% yield of 2-[4-(N-methyl)aminophenyl]oxazoline, mp 145-147° C. Following the Example 6 procedure,the aforesaid compound was treated with TDO to form the oxazoline shownbelow, having a methyl group attached to the nitrogen in theacetoacetanilide segment. The product was recrystallized from ethylacetate, mp 102-105° C. Elemental analysis, FT-IR, exhibiting 1726 (C—O)and 1635 (—C═N—) cm⁻¹ absorptions, and with ¹H NMR confirmed the belowdrawn structure.

[0064] This compound has the following structure:

EXAMPLE 10 N-[4-(4,4-dimethyl-2-oxazolin-2-yl)phenyl]acetoacetamide

[0065] Ethyl p-aminobenzoate, 20.65 g (0.125 mol),2-methyl-2-aminopropanol, 22.3 g (0.25 mol) 150 ml of xylene, and 0.25 gof lithium amide were combined and heated at the reflux temperature for50 hr. The alcohol and water liberated was collected in a Dean-Starktrap, providing indication when the reaction was complete. The xylenesolvent was removed and the viscous liquid was added to water toprecipitate the product. After drying, a 15.5 g (65%) yield of the4,4-dimethyl derivative of 4-aminophenyl oxazoline was obtained. Theproduct was recrystallized from ethyl acetate, giving white, crystallinematerial with mp 172° C. FT-IR, with peaks centered at 3445 (NH), 1635(—C═N—), and 1602 (phenyl) cm⁻¹ confirmed the desired aminofunctionalized oxazoline. Following the Example 6 procedure, TDO wasused to covert the aforesaid compound to the desired acetoacetamide. Thestructure of this new composition is as follows:

EXAMPLE 11 N-Methyl-N-[2-(2-oxazolin-2-yl)ethyl]acetoacetamide

[0066] 3-Methylaminopropionitrile, 50 g (0.59 mol), ethanolamine, 73.2 g(1.2 mol), 3.2 g of zinc acetate, and 100 ml xylene were combined andheated at reflux under nitrogen. When no more NH₃ was detected comingfrom the reaction, the xylene was removed and the crude product purifiedby distillation, bp 80-82° C./45 mm Hg. The FT-IR, of the slightlyyellow colored liquid, showed a broad NE peak at 3370 cm⁻¹ and theexpected —C═N-peak at 1637 cm⁻¹, supporting preparation of the desiredintermediate 2-[2-(N-methyl-amino) ethyl] oxazoline. Using the Example 6procedure, the aforesaid intermediate was treated with a slight molarexcess of TDO in xylene solvent, obtaining the desiredN-methyl-N-[2-(2-oxazolin-2-yl)ethyl] acetoacetamide as a yellow coloredliquid. The FT-IR, with peaks centered at 3304, 2941, 1718, and 1649cm⁻¹, and ¹H NMR spectra supported the following structure.

EXAMPLE 12 Acetylacetonate Derivative of 2-(3-Hydroxypropyl)oxazoline

[0067] The compound 3-hydroxypropyl-2-oxazoline was prepared bytechniques known in the patent (1 1) literature. A reaction flask wascharged with 10.6 g (0.5mol) of 3-hydroxypropyl-2-oxazoline, 11.4 g(0.08 mol) of TDO, and 100 ml of xylene. Heating with stirring undernitrogen at the reflux temperature of xylene for 6 hr. followed byremoval of volatiles, gave a viscous oil. The FT-IR and ¹H NMR spectrawere supportive of the following structure.

EXAMPLE 13 Acetylacetonate Derivative of 2-(3-Hydroxypentyl)oxazoline

[0068] Using the technique outlined in Example 12, 2-(5-hydroxypentyl)oxazoline was prepared and treated with excess TDO to obtain a goodyield of the desired acetylacetonate derivative shown below. The FT-IRand ¹H NMR confirmed the following structure.

EXAMPLE 14 Acetylacetonate Derivative of2-(p-Hydroxyethoxyphenyloxazoline)

[0069] A 250 ml. round bottom, three-neck flask was charged with2-(p-hydroxyethoxyphenyl) oxazoline, 8.28 g (0.04 mol TDO, 11.36 g (0.08mol) and 120 ml of xylene. The solution was stirred and heated atreflux, under nitrogen, for 5 hr. Evaporation of the solvent gave a highyield of the crude, solid product. After washing with ethyl acetate, theproduct was recrystalized from petroleum ether to give a good yield ofthe desired compound, mp 72-75° C. Elemental analysis, FT-IR and ¹H NMRspectra supported the structure shown below.

EXAMPLE 15 Acetylacetate Derivative of the Butyrolactamide

[0070] The monomer 2-(4-aminophenyl)oxazoline was combined and heatedunder nitrogen with a slight excess of butyrolactone, giving anexcellent yield of the desired hydroxyalkyl substituted amide of thestarting aminophenyl oxazoline compound. The latter composition wastreated with an excess of TDO to obtain the compound with the followingstructure in excellent yield, with structure confirmed by FT-IR and ¹HNMR spectroscopy.

EXAMPLE 16 Acetoacetate Derivative of the Hydroxyethyl carbamateprepared from 2-(4-Aminophenyl) oxazoline

[0071] 4-APOXO was treated with a slight molar excess of ethylenecarbonate to prepare the following carbamate, as shown:

[0072] The above compound, which is unknown to the literature, wastreated with a slight excess of diketene, per Example 4, to prepare inexcellent yield the desired acetoacetate monomer, with structure shownbelow confirmed by FT-IR and ¹H NMR spectroscopy.

EXAMPLE 17 Polymerization of 2-(4-acetoacetanilide)oxazoline (4-AAOXO)

[0073] The monomer 4-AAOXO, 4.0g, and anisole (50 ml) solvent, alongwith a catalytic amount (0.15 g.) of the cationic polymerizationinitiator, methyl tosylate (TsOCH₃), were combined under nitrogen andsealed in a small reaction flask containing a magnetic stir bar. Withstirring, the polymerization was run for 10 hr at 135° C. After cooling,the anisole solution was combined with hexane to precipitate thepolymer. After collection and drying under vacuum at 45° C., the poly(4-AAOXO), soluble with difficulty in N, N-dimethylformamide (DMF), wasobtained in essentially quantitative yield. The polymer structure wasconfirmed by FT-IR and ¹H NMR analysis. Polymerization under the sameprocedure with acetonitrile solvent and SnCl₄ initiator produced poly(4-AAOXO) which was readily soluble in DMF.

EXAMPLE 18 Copolymerization of 2-(4-acetoacetanilide) oxazoline(4-AAOXO) with 2-phenyloxazoline

[0074] The monomer 2-(4-acetoacetanilide) oxazoline [4-AAOXO], 2.5 g.and 2-phenyloxazoline (2.5g.), with 0.15 g of TsOCH₃ were mixed in asmall glass vial containing 45 ml of anisole. The vial was flushed withnitrogen, sealed, and placed in a thermostatted bath at 120° C. for 13hr. The polymer solution, after cooling, was combined with vigorouslystirred petroleum ether to precipitate the copolymer. The copolymer wascollected, washed with petroleum ether, and dried under vacuum at 45° C.FT-IR and ¹H NMR spectra confirmed the copolymer contained both monomerresidues.

EXAMPLE 19 Copolymerization of 4-AAOXO with ethyl oxazoline

[0075] Using the procedure described in Example 18, a copolymer of4-AAOXO and 2-ethyloxazoline was produced and isolated in high yield.FT-IR and ¹H NMR confirmed that the copolymer contained both monomerresidues.

EXAMPLE 20 Copolymerization of 3-AAOXO with 2-phenyloxazoline

[0076] Using Example 18 procedure, the copolymer of 3-AAOXO and2-phenyloxazoline was obtained in high yield. FT-IR confirmed that thecopolymer contained both monomer residues.

[0077] The desired molecular weights for the copolymers of Examples 19and 20 are in the range of 6,000-25,000.

EXAMPLE 21 Copolymerization of 4-AAOXI with 2-phenyloxazoline

[0078] Using Example 18 procedure, the copolymer of 4-AAOXI and2-phenyloxazoline was obtained in high yield. FT-IR and ¹H NMR confirmedthat the copolymer contained both monomer residues.

[0079] While Example 19 illustrates the copolymerization of 4-AAOXO withethyl oxazoline, it is obvious that the corresponding oxazine compoundscould be employed.

EXAMPLE 22 Formulation

[0080] Aqueous formulations of the compounds of this invention can beproduced by copolymerizing the compounds with ethyl oxazoline.Specifically the ethyl oxazoline should be present in an amount of 90mole percent. When 4-AAOXO was employed, these solutions can be mixedwith a crosslinker and drawn down over any substrate.

INDUSTRIAL APPLICABILITY

[0081] The monomers of this invention when further crosslinked at roomtemperature result in polymers useful in coatings, inks, overprintvarnishes, and surface treatment applications.

That which is claimed is:
 1. A compound having the formula:

wherein R is an alkyl group containing 1-5 carbon atoms or an aryl,substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl,alkylether-aryl or O; R₁ and R₂ are hydrogen or a methyl group; X is O,NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, orO—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl, NR″ is O-alkyl-ONH, or

wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.2. The compound of claim 1 wherein R is aryl, X is NH, NR or NR′, R₁ andR₂ are hydrogen or a methyl group and n is 0 or
 1. 3. The compound ofclaim 1 wherein R is aryl, X is NH, R₁ and R₂ are hydrogen and n is 0.4. The compound of claim 1 wherein R is aryl, X is NH, R₁ and R₂ arehydrogen and n is
 1. 5. The compound of claim 1 wherein R is aryl, X isNR′, R₁ and R₂ are hydrogen and n is
 0. 6. The compound of claim 5wherein R′ is methyl.
 7. The compound of claim 1 wherein R is aryl, X isNH, R₁ and R₂ are CH₃ and n is
 0. 8. The compound of claim 1 wherein Ris an alkyl group, X is NR′, R₁ and R₂ are hydrogen and n is
 0. 9. Thecompound of claim 8 wherein R is ethyl.
 10. The compound of claim 8wherein R′ is methyl.
 11. The compound of claim 1 wherein R is an alkylgroup, X is O alkyl, R₁ and R₂ are hydrogen and n is
 0. 12. The compoundof claim 11 wherein O-alkyl is O-propyl.
 13. The compound of claim 11wherein O-alkyl is O-pentyl.
 14. The compound of claim 11 whereinO-alkyl is O-methyl.
 15. The compound of claim 1 wherein R is aryl, X isO-alkyl-O, R₁ and R₂ are hydrogen and n is
 0. 16. The compound of claim15 wherein O-alkyl-O is O-ethyl-O.
 17. The compound of claim 1 wherein Ris aryl, X is O-alkyl-ONH, R₁ and R₂ are hydrogen and n is
 0. 18. Thecompound of claim 17 wherein O-alkyl-ONH is butyrolactamide.
 19. Thecompound of claim 1 wherein R is aryl, X is

R₁ and R₂ are hydrogen and n is
 0. 20. The compound of claim 19 wherein


21. A polymer or copolymer comprising an oxazoline or oxazine ringopening

wherein R is an alkyl group containing 1-5 carbon atoms or an aryl,substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl,alkylether-aryl or O; R₁ and R₂ are hydrogen or a methyl group; X is O,NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, orO—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl, NR″ is O-alkyl-ONH, or

wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.22. The polymer or copolymer of claim 21 wherein R is aryl, X is NH, NRor NR′, R₁ and R₂ are hydrogen or a methyl group and n is 0 or
 1. 23.The polymer or copolymer of claim 21 wherein R is aryl, X is NH, R₁ andR₂ are hydrogen and n is
 0. 24. The polymer or copolymer of claim 21wherein R is aryl, X is NH, R₁ and R₂ and hydrogen and n is
 1. 25. Thepolymer or copolymer of claim 21 wherein R is aryl, X is R′, R₁ and R₂are hydrogen and n is
 0. 26. The polymer or copolymers of claim 25wherein R′ is methyl.
 27. The polymer or copolymer of claim 21 wherein Ris aryl, X is NH, R₁ and R₂ are CH₃ and n is
 0. 28. The polymer orcopolymer of claim 21 wherein R is an alkyl group, X is NR′, R₁ and R₂are hydrogen and n is
 0. 29. The polymer or copolymer of claim 28wherein R is ethyl.
 30. The polymer or copolymer of claim 28 wherein R′is methyl.
 31. The polymer or copolymer of claim 21 wherein R is analkyl group, X is O-alkyl, R₁ and R₂ are hydrogen and n is
 0. 32. Thepolymer or copolymer of claim 31 wherein O-alkyl is O-propyl.
 33. Thepolymer or copolymer of claim 31 wherein O-alkyl is O-pentyl.
 34. Thepolymer or copolymer according to claim 31 wherein O-alkyl is O methyl.35. The polymer or copolymer of claim 21 wherein R is aryl, X isO-alkyl-O, R₁ and R₂ are hydrogen and n is
 0. 36. The polymer orcopolymer of claim 35 wherein O-alkyl-O is O-ethyl-O.
 37. The polymer orcopolymer of claim 21 wherein R is aryl, X is O-alkyl-ONH, R₁ and R₂ arehydrogen and n is
 0. 38. The polymer or copolymer of claim 37 whereinO-alkyl-ONH is butyrolactamide.
 39. The polymer or copolymer accordingto claim 21 wherein R is aryl, X is

R₁ and R₂ are hydrogen and n is
 0. 40. The polymer or copolymer of claim39 wherein


41. An aqueous formulation comprising (a) a polymeric ingredient havingan oxazoline or oxazine ring opening moiety derived from a compoundhaving the formula:

wherein R is an alkyl group containing 1-5 carbon atoms or an aryl,substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl,alkylether-aryl or O; R₁ and R₂ are hydrogen or a methyl group; X is O,NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, orO—R″ or NR″ wherein O—R″ is O-alkyl-O or O-alkyl-, NR″ is O-alkyl-ONH,or

wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.42. The aqueous formulation of claim 41 wherein R is aryl, X is NH, NRor NR′, R₁ and R₂ are hydrogen or a methyl group and n is 0 or
 1. 43.The aqueous formulation of claim 41 wherein R is aryl, X is NH, R₁ andR₂ are hydrogen and n is
 0. 44. The aqueous formulation of claim 41wherein R is aryl, X is NH, R₁ and R₂ are hydrogen and n is
 1. 45. Theaqueous formulation of claim 41 wherein R is aryl, X is NR′, R₁ and R₂are hydrogen and n is
 0. 46. The aqueous formation of claim 45 whereinR′ is methyl.
 47. The aqueous formulation of claim 41 wherein R is aryl,X is NH, R₁ and R₂are CH₃ and n is
 0. 48. The aqueous formulation ofclaim 41 wherein R is an alkyl group, X is NR′, R₁ and R₂ are hydrogenand n is
 0. 49. The aqueous formulation of claim 48 wherein R is ethyl.50. The aqueous formation of claim 48 wherein R′ is methyl.
 51. Theaqueous formulation of claim 41 wherein R is alkyl, X is O-alkyl, R₁ andR₂ are hydrogen and n is
 0. 52. The aqueous formulation of claim 51wherein O-alkyl is O-propyl.
 53. The aqueous formulation of claim 51wherein O-alkyl is O-pentyl.
 54. The aqueous formulation of claim 51wherein O-alkyl is O-methyl.
 55. The aqueous formulation of claim 41wherein R is aryl, X is O-alkyl-O, R₁ and R₂ are hydrogen and is
 0. 56.The aqueous formulation of claim 55 wherein O-alkyl-O is O-ethyl-O. 57.The aqueous formulation of claim 41 wherein R is aryl, X is O-alkyl-ONH,R₁ and R₂ are hydrogen and n is
 0. 58. The aqueous formulation of claim57 wherein O-alkyl-O NH is butyrolactamide.
 59. The aqueous formulationof claim 41 wherein R is aryl, X is O-alkyl-

R₁ and R₂ are hydrogen and n is
 0. 60. The aqueous formulation of claim59 wherein

NH.